Oxalate/hydrogen peroxide chemiluminescence reaction. A 19F NMR probe of the reaction mechanism

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Abstract
The mechanism of the oxalate/hydrogen peroxide chemiluminescence reaction has been examined by magnetic resonance techniques. Investigation of the reactive intermediates involved in chemiluminescence was carried out with bis(2,6‐difluorophenyl)oxalate (DFPO) using 19F NMR to probe its reactions with aqueous hydrogen peroxide. Formation and reactions of the intermediate hydroperoxy oxalate ester B along with the formation of the half ester product C and difluorophenol D were monitored by 19F NMR. When the reaction of DFPO and aqueous hydrogen peroxide was carried out in the presence of dansylphenylalanine, a typical fluorescent analyte, the intensity of the resonance due to the intermediate B was diminished in direct proportion to the concentration of the analyte. Comparison of the time/intensity profile of the chemiluminescence emission with that of the 19F NMR transient suggests that the hydroperoxy oxalate ester B is the likely ‘reactive’ intermediate, capable of participating in a chemically initiated electron exchange luminescence mechanism.

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